Co-surfactants based on aldehydes

ABSTRACT

The present invention relates to cyclic cosurfactants which are produced by condensation reaction of C 3 -C 6 -aldehydes with polyfunctional alcohols, amines, thiols or carboxylic acids and have the formulae I or II as given in the description. The cosurfactants are suitable for use in household detergents, household cleaners, body-cleansing compositions and bodycare compositions.

The present invention relates to condensation products of aldehydes withalcohols which have at least one other function from the group ofhydroxyl, diol, amino and carboxyl functions.

Surfactants are so-called amphiphilic molecules which have a hydrophobicmoiety and a hydrophilic moiety in their molecular structure. As aresult of this property, surfactants are able to form interfacial filmsand so-called micelles. These are aggregates of surfactants which formin aqueous solutions and can assume various forms (spheres, rods,disks). Micelles form above a certain concentration, the so-calledcritical micelle formation concentration (CMC). In addition, amphiphilicmolecules have the property of forming interfacial films betweenhydrophobic and hydrophilic phases and thus, for example, having anemulsifying or foaming action.

Cosurfactants likewise have amphiphilic properties, although these areinsufficient for being able to form micelles and interfacial films ontheir own. However, they are intercalated between the surfactants andbring about an increase in the packing density of the amphiphiles(surfactants and cosurfactants) in the structures formed thereby, suchas micelles or interfaces. As a result, not only are the criticalmicelle formation concentration and the surface tension reduced, butalso the interfacial tension between the aqueous surfactant solution andnonpolar substances such as, for example, oils, meaning that theabsorption capacity of the surfactant system for these substancesincreases to the point of the formation of microemulsions. This resultsin a high solubilizing and emulsifying power, a higher cleaningcapacity, and an increased stability of the emulsions and foams. Ifcosurfactants are used, micelles can be formed at a significantly lowersurfactant concentration.

Further effects which are brought about as a result of the use of thecosurfactants and the resulting enhanced aggregation tendency of theamphiphiles are known. This is, firstly, the aggregation transformationof spherical to anisometric micellar associates. This structural changein the micelles has effects on the rheology of the solutions containingthe micelles, in particular in dilute solutions. At the same time, inthe phase diagram, there is a shift of liquid crystalline structurespresent to lower concentrations, as a result of which a preferredformation of gel phases with higher packing density is observed.Consequently, even at concentrations of significantly <10% by weight,lamellar micelle structures arise which are otherwise observed only atsignificantly higher concentrations. A further interesting phenomenon isthe formation, in addition to the known liquid crystalline gel phases,of novel superstructures which have interesting application properties.Of particular interest here are vesicular phases and also so-called L₃phases which have a sponge-like construction and have microemulsion-likeproperties. They can be used in dilute concentration ranges to adjustthe viscosity.

The prior art describes a number of compounds or classes of compoundswhich are suitable as cosurfactants.

C₅-C₁₀-alcohols exhibit advantageous properties, but are often not useddue to their characteristic odor.

Alcohols with low degrees of ethoxylation, such as, for example, laurylalcohol ethoxylates with low degrees of ethoxylation, diethylene glycolmonohexyl ether or propylene glycol butyl ether, can lead to improvedemulsifying power or foam stability in some surfactant systems, but havetoo low a polarity of the head group for surfactant formulations with ahigh anionic surfactant content.

Fatty acid ethanolamines are used, for example, for adjusting theviscosity in shampoos. However, they are suspected of formingnitrosamines.

G. J. Smith describes in Seifen, Ölen, Fette, Wachse, 105 (1979, pages319 ff and 345 ff) the use of alkylamine oxides as cosurfactant invarious applications. These too are suspected of containingnitrosamines. Through a lengthy, complex preparation technology, thatcan be largely avoided.

Analogously to the amine oxides, other zwitterionic surfactants, suchas, for example, sulfobetaines or carboxylammoniobetaines, can also beused as cosurfactant. With these products, the formation of gel phaseshas proven to be very poor. Instead, however, they have the applicationadvantage that the skin irritancy of corresponding surfactant mixturesis reduced.

WO 98/00418 discloses alkylene carbonates and their use ascosurfactants.

In the applications known to date, the ratio of cosurfactants tosurfactants used varies, depending on the application, from about 1:20to 1:2. In some cases, such as, for example, alkylamine oxides, thecosurfactant may also be used in higher concentrations.

It is an object of the present invention to provide compounds suitableas cosurfactants which do not have said disadvantages, in particularexhibit better cost efficiency, and are environmentally compatible andfree from risks for humans.

We have found that this object is achieved by cyclic aldehydederivatives of the formulae

in which the symbols X, Y, Z and R¹ to R¹³ have the following meanings:

-   -   R¹ is hydrogen or a linear or branched, substituted or        unsubstituted C₃-C₂₉-alkyl group or a linear or branched,        substituted or unsubstituted C₃-C₂₉-alkenyl group, where one or        more carbon atoms in the alkyl or alkenyl chain may be replaced        by —O—, —NR¹⁴, —C(O)NR¹⁵— or —S— and —O—O— and —S—S— are        excluded;    -   R² is hydrogen or —CH₃;    -   R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from        the group of substituents consisting of: H; —CN; —C(O)OH;        —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; C₆H₅, in which one or more hydrogens        may be replaced by substituents;    -   and C₁-C₅-alkyl groups which, at any desired point in the chain,        may have 1 to 4 substituents from the group —OH; —SH; —CN;        NR¹⁶R¹⁷; —OR²²; or 1 to 2 substituents from the group consisting        of —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻;        OPO(OR²¹)₂; C₆H₅, in which one or more hydrogens may be replaced        by substituents; and        or    -   one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O;    -   R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, chosen        from the group of substituents consisting of: H; —CN; —NR¹⁶R¹⁷;        —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂;        C₆H₅, in which one or more hydrogens may be replaced by        substituents;    -   and C₁-C₅-alkyl groups which, at any desired point on the chain,        may have 1 to 4 substituents from the group —OH; —SH; —CN;        NR¹⁶R¹⁷; —OR²²; or 1 to 2 substituents from the group consisting        of —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻;        OPO(OR²¹)₂; C₆H₅, in which one or more hydrogens may be replaced        by substituents; and    -   R¹¹ has, independently, the same meaning as R¹;    -   R¹² has, independently, the same meaning as R²;    -   R¹³ has, independently, the same meaning as R³, R⁴, R⁵ or R⁶;    -   R¹⁴ is a linear or branched C₁-C₄-alkyl group;    -   R¹⁵ is hydrogen or a linear or branched C₁-C₄-alkyl group;    -   R¹⁶, R¹⁷ are, independently of one another, hydrogen or a linear        or branched C₁-C₄-alkyl group;    -   R¹⁸ is chosen from the group consisting of C₁-C₆-alkyl groups        and ethyleneoxy groups —(CH₂—CH₂O—)_(p);    -   R¹⁹, R²⁰ have, independently, the same meaning as R¹⁶, R¹⁷;    -   R²¹ is a C₁-C₄-alkyl group or —C₆H₅;    -   R²² is chosen from the group consisting of C₁-C₁₀-alkyl groups,        acyl groups —C(O)R²³ and the group consisting of ethyleneoxy        groups —(CH₂—CH₂O—)_(q), propyleneoxy groups        —(CH(CH₃)—CH₂O—)_(r), butyleneoxy groups —(C₄H₉O—)_(s), and        alkyleneoxy groups containing at least two of the abovementioned        groups in the form of block or random copolymers and containing        a total of at most 15 alkyleneoxy units;    -   R²³ is a C₁-C₁₈-alkyl group;    -   X and Y in formula I and II are, independently of one another,        O, S, or NR²⁴, Z in formula II is N;    -   R²⁴ is hydrogen or a C₁-C₄-alkyl group;    -   l, m and n are, independently of one another, 0 or 1;    -   p is an integer from 1 to 15;    -   q is an integer from 1 to 15;    -   r is an integer from 1 to 15;    -   s is an integer from 1 to 15;    -   and where the aliphatic moiety of the compounds of the formula I        or II which does not originate from the feed aldehyde, in cases        where X, Y are ═O and R³, R⁴ or R⁵, R⁶ are ═O, must have at        least 2 carbon atoms, and in all other cases must have at least        3 carbon atoms.

The compounds of the formulae I and II are highly suitable for use ascosurfactants in the customary washing and cleaning formulations knownto the person skilled in the art.

The compounds according to the formulae I and II are prepared bycondensation of aldehydes with polyfunctional compounds whose functionalgroups are chosen from the group of hydroxyl, thiol, carboxyl andprimary and secondary amino functions. There must be at least twofunctional groups, which may be identical or different, present in thepolyfunctional compound.

The aldehydes to be used are linear or branched aliphaticC₄-C₃₀-aldehydes, preferably C₆-C₁₈-aldehydes. These aldehydes have anaverage degree of branching of from 0 to 2.5, preferably 0.2 to 1.6. Thedegree of branching here is defined as (number of methyl groups permolecule) −1. Since the aliphatic chain radical of the aldehyde joinedto the carbonyl function corresponds to the radical R¹ in the formulae Iand II, this last-named radical also has a corresponding degree ofbranching. The alkyl chain can have further substituents which increasethe suitability of the molecule as a cosurfactant, or at least do notadversely affect it. Such substituents are known to the person skilledin the art. Preferably, no further substituents are present on the alkylchain. Examples of aldehydes which can be used include butanal,pentanal, hexanal, heptanal, octanal, nonanal, decanal, undecanal,dodecanal, tridecanal, tetradecanal and hexadecanal. For all of theabovementioned aldehydes, it is possible to use either the unbranchedn-form or branched isomers. In general, use is made of isomer mixturesof the aldehydes used which have the desired average degree ofbranching.

It is also possible to use mixtures of aldehydes of varying carbonnumber and to use the resulting product mixtures as cosurfactants. Thisembodiment is preferred in accordance with the invention. Particularpreference is given here to the use of a mixture of C₁₂-C₁₄-aldehydes.

Also preferred in accordance with the invention is the use of theso-called Guerbet aldehydes and their unsaturated analogs. These arealdehydes with branching in the 2 position. Examples include2-ethylhexanal, 2-ethylhex-2-enal, 2-propylhexanal, 2-propylheptanal,2-propylhept-2-enal, 2-butyloctanal, 2-butyloct-2-enal, 2-pentylnonanaland 2-pentylnon-2-enal. Saturated aldehydes are preferred.

The polyfunctional starting materials to be reacted with the aldehydeare the substances listed below.

Polyols:

Suitable polyols are linear and branched aliphatic C₃-C₆-polyols with atleast two hydroxyl functions, preferably 2 to 5 hydroxyl functions, inparticular 2 to 4 hydroxyl functions. As well as the hydroxyl functions,further functional groups may be present which are chosen from the group—SH; —CN; NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻;—OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; C₆H₅, in which one or more hydrogens may bereplaced by substituents; and

Examples of suitable polyols include glycerol, tartaric acid, diethyltartrate, trimethylolpropane, fructose, cyclohexanediol, sucrose,tetrahydroxybutane.

Alkanolamines:

Suitable alkanolamines are linear and branched aliphaticC₃-C₆-alkanolamines with at least one primary or secondary aminofunction and one hydroxyl function. A maximum of 4 further hydroxyl oramino functions may be present, preferably the alkanolamine has exactlyone amino function. Further substituents may be present from the group:—SH; —CN; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻;OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or more hydrogens may be replacedby substituents; and

Examples of suitable alkanolamines include trimethylolmethylamine,diethanolamine, propanolamine, dipropanolamine, amino sugars, aminoacids, such as, for example, sarcosine, serine and threonine.

Thiols:

Suitable thiols are linear and branched aliphatic C₃-C₆-thiols with onethiol function and one hydroxyl function. Four further hydroxyl or thiolfunctions may be present. Preferably, the thiol has exactly one SHfunction. Further substituents may be present from the group: —OH; —SH;—CN; NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or more hydrogens may bereplaced by substituents; and

Examples of suitable thiols are mercaptoethanol, mercaptolactic acid,mercaptoglycolic acid, thiosalicylic acid, mercaptosuccinic acid,3-mercapto-1,2-propanediol, cysteine, N-acetylcysteine,3-mercaptopropionic acid, penicillamine, dithiothreitol.

Hydroxycarboxylic Acids:

Suitable hydroxycarboxylic acids are linear and branched aliphaticC₃-C₆-hydroxycarboxylic acids with one hydroxyl function and onecarboxyl function. Four further hydroxyl or carboxyl functions may bepresent. Preferably, the molecule has exactly one carboxyl function.Further substituents may be present from the group: —SH; —CN; NR¹⁶R¹⁷;—C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²;—C₆H₅, in which one or more hydrogens may be replaced by substituents;and

Examples of suitable hydroxycarboxylic acids include lactic acid, citricacid, glycolic acid, tartaric acid, glyceric acid, malic acid andsalicylic acid.

Diamines:

It is possible to use linear and branched aliphatic C₃-C₆-diamineshaving 2 to 6 primary or secondary amino functions. Preferably, thediamines have 2 to 4 primary or secondary amino functions. Furthersubstituents may be present from the group: —OH; —SH; —CN; —C(O)OH;—C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²;—C₆H₅, in which one or more hydrogens may be replaced by substituents;and

Examples of suitable diamines include propylenediamine,triethylenetriamine, triethylenetetramine, N-aminopropylethylenediamine(N₃-amine) and N,N′-bis(aminopropyl)ethylenediamine (N₄ amine),hydroxyethylethylenediamine.

Aminothiols:

Suitable aminothiols are linear and branched aliphatic C₃-C₆-aminothiolswith at least one primary or secondary amino function and one thiolfunction. Preferably, the amino thiol used has exactly one primary orsecondary amino function and exactly one thiol function. Furthersubstituents may be present from the group: —OH; —CN; —C(O)OH;—C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²;—C₆H₅, in which one or more hydrogens may be replaced by substituents;and

Examples include cysteine and tyrosine and mercaptopropylamine.

Amino Acids:

Suitable amino acids are linear and branched aliphatic C₃-C₆-amino acidswith at least one primary or secondary amino function and one carboxylfunction. Preferably, the amino acids used according to the inventioncontain one primary or secondary amino function. Examples includeiminodiacetic acid HN(CH₂CO₂H)₂ and ethylenediamine triacetic acid, andthe amino acids alanine, arginine, asparagine, aspartic acid, cysteine,glutamine, glutaminic acid, glycine, histidine, isoleucine, leucine,lysine, methionine, phenylalanine, proline, serine, threonine,tryptophan, tyrosine, valine and N-phosphonomethylglycine.

Dithiols:

Suitable dithiols are linear and branched aliphatic C₃-C₆-dithiols withat least two thiol functions. Preferably, the dithiol has exactly twothiol functions. Further substituents may be present from the group:—OH; —CN; NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻;OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or more hydrogens may bereplaced by substituents; and

The alkyleneoxy substituents which may be present in the cosurfactantsof the formulae I and II used according to the invention (see, forexample, definition of R²²) may be pure ethyleneoxy, propyleneoxy orbutyleneoxy substituents. Butyleneoxy substituents may be those derivedfrom 1-butene, 2-butene or isobutene. Within the group of butyleneoxysubstituents, preference is given to the group —(CH₂CH(C₂H₅)—O) derivedfrom 1-butene. These substituents can, however, also consist of mixturesof ethyleneoxy, propyleneoxy or butyleneoxy units, for example as arandom oligo/polymer or as a block copolymer. Preferably, saidalkyleneoxy substituents are pure ethyleneoxy groups or terminallycapped ethyleneoxy groups.

If an individual compound is present which contains alkyleneoxysubstituents, then this contains a whole-number amount of alkyleneoxyunits in the amounts given in the description. If mixtures of differentcompounds with alkyleneoxy substituents are present, these are oftenmixtures in which the amount of alkyleneoxy substituents is, on average,no longer a whole number.

—C₆H₅ designates a phenyl group.

Preferred molecules of the formulae I and II are those in which one ormore of the symbols X, Y and Z, one or more of the substituents R¹ toR¹³, and one or more of the symbols l, m and n have the followingmeanings:

-   -   R¹ is a linear or branched C₅-C₁₇-alkyl group or a linear or        branched C₃-C₁₇-alkenyl group, where one or more carbon atoms in        the alkyl chain may be replaced by O or NR¹⁴ and —O—O— is        excluded;    -   R² is —H;    -   R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from        the group consisting of: —H; —C(O)OH; —C(O)OR¹⁸;    -   and C₁-C₅-alkyl groups which, at any desired position on the        chain, may have 1 or 2 substituents from the group —OH; —CN;        NR¹⁶R¹⁷; —OR²²; or 1 substituent from the group consisting of        —C(O)OH; —C₆H₅, in which one or more hydrogens may be replaced        by substituents; and        or    -   one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O;    -   R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, chosen        from the group consisting of: —H; —NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸;    -   and C₁-C₅-alkyl groups which, at any desired position on the        chain, may have 1 or 2 substituents from the group —OH; —CN;        NR¹⁶R¹⁷; —OR²²; or 1 substituent from the group consisting of        —C(O)OH; —C₆H₅, in which one or more hydrogens may be replaced        by substituents; and    -   R¹¹ has, independently, the same meaning as R¹;    -   R¹² has, independently, the same meaning as R²;    -   R¹³ has, independently, the same meaning as R³, R⁴, R⁵ or R⁶;    -   R¹⁴ is a linear or branched C₁-C₄-alkyl group;    -   R¹⁶, R¹⁷ are, independently of one another, hydrogen or a linear        or branched C₁-C₄-alkyl group;    -   R¹⁸ is chosen from the group consisting of C₁-C₆-alkyl groups        and ethyleneoxy groups —(CH₂—CH₂O—)_(p);    -   R²² is chosen from the group consisting of C₁-C₄-alkyl groups,        acyl groups —C(O)R²³ and the group consisting of ethyleneoxy        groups —(CH₂—CH₂O—)_(q), propyleneoxy groups        —(CH(CH₃)—CH₂O—)_(r) and butyleneoxy groups —(C₄H₉O—)_(s), and        mixed alkyleneoxy groups;    -   R²³ is a C₁-C₁₈-alkyl group;    -   X and Y in the formula I and II are, independently of one        another, O or NR²⁴, Z in formula II is N;    -   R²⁴ is hydrogen or a C₁-C₄-alkyl group;    -   l, m and n are, independently of one another, 0 or 1;    -   p is an integer from 1 to 15;    -   q is an integer from 1 to 10;    -   r is an integer from 1 to 10;    -   s is an integer from 1 to 10;    -   and where the aliphatic moiety of the compounds of the formula I        or II which does not originate from the feed aldehyde, in cases        where X, Y are ═O and R³, R⁴ or R⁵, R⁶ are ═O, must have at        least 2 carbon atoms, and in all other cases must have at least        3 carbon atoms.

In this connection, it is preferred if all of the substituents R¹ to R¹³and symbols X, Y and Z and l, m, and n have the meanings given above.

More preferred are also the compounds of the formulae I and II, in whichone or more of the symbols X, Y, Z and l, m, and n and also one or moreof the substituents R¹ to R¹³ have the following meanings:

-   -   R¹ is a linear or branched C₅-C₁₇-alkyl group or a linear or        branched C₅-C₁₇-alkenyl group;    -   R² is —H;    -   R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from        the group consisting of: —H; —C(O)OH; and C₁-C₃-alkyl groups        which can have, at any desired point on the chain, 1 or 2        substituents from the group —OH; —NR¹⁶R¹⁷; —OR²²; or 1        substituent from the group consisting of —C(O)OH; and        or    -   one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O;    -   R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, chosen        from the group consisting of: —H; —NR¹⁶R¹⁷; —C(O)OH; and        C₁-C₃-alkyl groups which, at any desired point on the chain, can        have 1 or 2 substituents from the group —OH; NR¹⁶R¹⁷; or 1        substituent from the group consisting of —C(O)OH; and    -   R¹¹ has, independently, the same meaning as R¹;    -   R¹² has, independently, the same meaning as R²;    -   R¹³ has, independently, the same meaning as R³, R⁴, R⁵ or R⁶;    -   R¹⁶, R¹⁷ are, independently of one another, hydrogen or a linear        or branched C₁-C₄-alkyl group;    -   R²² is chosen from the group consisting of C₁-C₄-alkyl groups,        acyl groups —C(O)R²³ and the group consisting of ethyleneoxy        groups —(CH₂—CH₂O—)_(q), propyleneoxy groups        —(CH(CH₃)—CH₂O—)_(r) and butyleneoxy groups        —(CH₂CH(C₂H₅—O—)_(s), and mixed alkyleneoxy groups;    -   R²³ is a C₁-C₁₈-alkyl group;    -   X and Y in formula I and II are, independently of one another, O        or NR²⁴, Z in formula II is N;    -   R²⁴ is hydrogen or a C₁-C₄-alkyl group;    -   l, m and n are, independently of one another, 0 or 1;    -   q is an integer from 1 to 10;    -   r is an integer from 1 to 10;    -   s is an integer from 1 to 10;    -   and where the aliphatic moiety of the compounds of the formula I        or II which does not originate from the feed aldehyde in cases        where X, Y are ═O and R³, R⁴ or R⁵, R⁶ are ═O must have at least        2 carbon atoms, and in all other cases must have at least 3        carbon atoms.

In this connection, it is preferred if all of the substituents R¹ to R¹³and the symbols X, Y and Z and l, m, and n have the meanings givenabove.

Even more preferred are also the compounds of the formulae I and II inwhich one or more of the symbols X, Y, Z and l, m, and n and also one ormore of the substituents R¹ to R¹³ have the following meanings:

-   -   R¹ is a linear or branched C₃-C₂₁-alkyl group or a linear or        branched C₃-C₂₁-alkenyl group;    -   R² is —H;    -   R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from        the group consisting of: —H; —C(O)OH; and C₁-C₃-alkyl groups        which may have, at any desired point on the chain, 1 or 2        substituents from the group —OH; —NR¹⁶R¹⁷; —OR²²; or 1        substituent of the type —C(O)OH; or    -   one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O;    -   R⁷, R⁸, R⁹ and R¹⁰ are, independently of one another, chosen        from the group consisting of: —H; —NR¹⁶R¹⁷; —C(O)OH; and        C₁-C₃-alkyl groups which may have, at any desired point on the        chain, 1 or 2 substituents from the group —OH; NR¹⁶R¹⁷; or 1        substituent of the type —C(O)OH;    -   R¹¹ has, independently, the same meaning as R¹;    -   R¹² has, independently, the same meaning as R²;    -   R¹³ has, independently, the same meaning as R³, R⁴, R⁵ or R⁶;    -   R¹⁶, R¹⁷ are, independently of one another, hydrogen or a linear        or branched C₁-C₄-alkyl group;    -   R²² is chosen from the group consisting of C₁-C₄-alkyl groups        and ethyleneoxy groups —(CH₂—CH₂O—)_(q);    -   X and Y in formula I and II are, independently of one another,        O, S, or NR²⁴, Z in formula II is N;    -   R²⁴ is hydrogen or a C₁-C₄-alkyl group;    -   l, m and n are, independently of one another, 0 or 1;    -   q is an integer from 3 to 8;    -   and where the aliphatic moiety of the compounds of the formula I        or II which does not originate from the feed aldehyde in cases        where X, Y are ═O and R³, R⁴ or R⁵, R⁶ are ═O must have at least        2 carbon atoms, and in all other cases must have at least 3        carbon atoms.

In this connection, it is preferred if all of the substituents R¹ to R¹³and the symbols X, Y and Z and l, m, and n have the meanings givenabove.

Particular preference is given to the following compounds:

-   -   4,4-di(hydroxymethyl)-2-nonyloxazolidine    -   and    -   2-(1-propylhexyl)4,4-di(hydroxymethyl)oxazolidine (6);    -   7a-hydroxymethyl-3,5-di(dodecyl)dihydrooxazolo[3,4-c]oxazole        (7);    -   7a-hydroxymethyl-3,5-di(tetradecyl)dihydrooxazolo[3,4-c]oxazole        (8);    -   7a-hydroxymethyl-3,5-di(undecyl)dihydrooxazolo[3,4-c]oxazole        (9);    -   7a-hydroxymethyl-3,5-di(tridecyl)dihydrooxazolo[3,4-c]oxazole        (10);    -   4,4-di(hydroxymethyl)-2-dodecyloxazolidine (11);    -   4,4-di(hydroxymethyl)-2-tetradecyloxazolidine (12);    -   4,4-di(hydroxymethyl)-2-undecyloxazolidine (13);    -   4,4-di(hydroxymethyl)-2-tridecyloxazolidine (14);    -   2-(1-propylhexyl)-[1,3]-dioxolan-4-one (15)

Mixtures of (9) and (10), mixtures of (13) and (14), mixtures of (7) and(8) and mixtures of (11) and (12) are likewise the subject-matter of themost preferred embodiment of the present invention.

A subject-matter of the most preferred embodiment of the presentinvention are likewise the adducts of the compounds (1) to (18) having 3to 10 ethylene oxide units and mixtures thereof. In connection with thepresent invention, the term “mixtures” is understood as meaning bothmixtures of adducts of a compound (1) to (18) with varying amounts ofadded ethylene oxide units, and also mixtures of ethylene oxide adductsof various compounds (1) to (18).

The invention further provides for the use of the compounds of theformulae I and II and the preferred compounds derived therefrom asspecified above as cosurfactant.

The compounds of the formulae I and II used according to the inventionas cosurfactants are prepared by customary condensation reactions knownto the person skilled in the art. The aldehyde and the substance or thesubstance mixture to be reacted therewith, which is chosen from theabovementioned group of substances, are, optionally in the presence of asuitable acid, reacted together in a suitable solvent, such as, forexample, toluene, chloroform or methylene chloride. Suitable acids arethe customary Lewis and Brönsted acids known to the person skilled inthe art which can be used in gaseous, liquid or solid form. Examplesinclude HCl, sulfuric acid, p-toluenesulfonic acid, p-toluenesulfonicacid pyridinium salt and acidic ion exchangers, for example Amberlyst®15and Serdolit Red. Alternatively, the starting material to be reactedwith the aldehyde can be added to an initial charge of the aldehyde,which may be dissolved in a solvent. This is advantageous particularlyin the case of hydroxycarboxylic acids, which can be added as aqueoussolution to the reaction mixture. Preferably, the water which formsduring the condensation is separated off by distillation. Preference isgiven to working without solvents. If a solvent is used, the water canbe separated off by azeotropic distillation, for example using a waterseparator.

The substances of the formulae I and II according to the invention to beused as cosurfactants are suitable for use in industrial, institutionalor domestic detergents and cleaners, and also in the so-called bodycaresector, namely body-cleansing and bodycare compositions.

Further applications are:

-   -   humectants, in particular for the printing industry.    -   cosmetic, pharmaceutical and crop protection formulations.        Suitable crop protection formulations are described, for example        in EP-A-0 050 228. Further ingredients customary for crop        protection compositions may also be present.    -   paints, coating compositions, inks, pigment preparations and        adhesives in the coating and polymer film industry.    -   leather fat-liquoring compositions.    -   formulations for the textile industry, such as leveling agents        or formulations for yarn cleaning.    -   fiber processing and auxiliaries for the paper and pulp        industry.    -   metal processing, such as metal refining and electroplating        sector.    -   food industry.    -   water treatment and drinking water production.    -   fermentation.    -   mineral processing and dust control.    -   building auxiliaries.    -   emulsion polymerization and preparation of dispersions.    -   coolants and lubricants.

The detergents are in solid, liquid, gel or paste form. The materials insolid form include powders and compacts, for example granulates andshaped bodies such as tablets.

The detergents comprise 0.1 to 40% by weight, in particular 0.5 to 30%by weight, very particularly 1 to 20% by weight, based on the totalamount of the formulation, of at least one substance of the formulae Iand/or II. Further constituents are listed below.

Detergent formulations usually comprise ingredients such as surfactants,builders, fragrances and dyes, complexing agents, polymers and otheringredients. Typical formulations are described, for example, in WO01/32820. Further ingredients suitable for various applications aredescribed in EP-A-0 620 270, WO 95/27034, EP-A-0 681 865, EP-A-0 616026, EP-A-0 616 028, DE-A-42 37 178 and U.S. Pat. No. 5,340,495, forexample.

For the purposes of this invention, detergents are generally used forthe washing of materials of greater or lesser flexibility, preferablythose which contain or consist of natural, synthetic or semisyntheticfiber materials and which consequently usually have at least partially atextile character. The materials which contain or consist of fibers can,in principle, be in any form which exists in use or for the preparationand processing. For example, fibers may be unarranged in the form ofstaple or aggregate, arranged in the form of threads, yarns, twines, orin the form of fabrics, such as nonwovens, loden materials or felt,wovens, knits in all conceivable types of weave.

These may be raw fibers or fibers in any stages of processing and may benatural protein or cellulose fibers, such as wool, silk, cotton, sisal,hemp, coconut fibers or synthetic fibers, such as, for example,polyester, polyamide or polyacrylonitrile fibers.

Detergents comprising cosurfactants according to the invention can alsobe used for cleaning fiber-containing materials, such as e.g. backedcarpets with cut or uncut pile.

The compositions of the detergents are preferably adapted to thedifferent purposes, as is familiar to the person skilled in the art fromthe prior art. For this purpose, all auxiliaries and additivescorresponding to the purpose and known from the prior art can be addedto the detergents.

In addition to the cosurfactants according to the invention, thefollowing may, for example, be present in detergents:

-   -   builders and cobuilders, such as polyphosphates, zeolites,        polycarboxylates, phosphonates or complexing agents    -   ionic surfactants, such as alcohol sulfates/ether sulfates,        alkylbenzenesulfonates, α-olefinsulfonates and other alcohol        sulfates/ether sulfates    -   nonionic surfactants, alcohol alkoxyates such as alkylamine        alkoxylates, alkyl polyglucosides    -   optical brighteners    -   color transfer inhibitors, such as polyvinylpyrrolidone of molar        masses 8000 to 70 000, vinylimidazole/vinylpyrrolidone        copolymers with a molar ratio of the monomers of from 1:10 to        2:1 and molar masses of from 8000 to 70 000, and        poly-4-vinylpyridine N-oxides with molar masses of from 8000 to        70 000    -   extenders, such as sodium sulfate or magnesium sulfate    -   soil release agent    -   incrustation inhibitors    -   bleaching systems, comprising bleach, such as perborate,        percarbonate and bleach activators, such as        tetraacetylethylenediamine, and also bleach stabilizers    -   perfume (oils)    -   foam suppressors, such as silicone oils    -   enzymes, such as amylases, lipases, cellulases, proteases    -   alkali metal donors, such as soluble alkali metal silicates,        e.g. pentasodium methasilicate, sodium carbonate.

Solvents, such as ethanol, isopropanol, 1,2-propylene glycol, butylglycol etc., can, for example, additionally be used in liquiddetergents.

In tablet detergents, it is additionally possible to use tabletingauxiliaries, such as polyethylene glycols with molar masses of more than1000 g/mol, polymer dispersions, and tablet disintegrants, such ascellulose derivatives, crosslinked polyvinylpyrrolidone, crosslinkedpolyacrylates or combinations of acids, such as citric acid and sodiumbicarbonate. A detailed list of possible ingredients is given below.

In some cases, it may be expedient to combine the cosurfactants usedaccording to the invention with other cosurfactants or with amphotericsurfactants, such as, for example, alkylamine oxides, or betaines.

Another class of nonionic surfactants are alkyl polyglucosides having 6to 22, preferably 10 to 18, carbon atoms in the alkyl chain. Thesecompounds generally contain 1 to 20, preferably 1.1 to 5, glucosideunits.

Another class of nonionic surfactants are N-alkylglucamides of thestructures

where B¹ is a C₆- to C₂₂-alkyl, B² is hydrogen or C₁- to C₄-alkyl and Dis a polyhydroxyalkyl radical having 5 to 12 carbon atoms and at least 3hydroxyl groups. Preferably, B¹ is C₁₀- to C₁₈-alkyl, B² is CH₃ and D isa C₅- or C₆-radical. For example, such compounds are obtained by theacylation of reductively aminated sugars with acid chlorides of C₁₀- toC₁₈-carboxylic acids.

Further suitable nonionic surfactants are the terminally capped fattyacid amide alkoxylates, known from WO-A 95/11225, of the formulaR¹—CO—NH—(CH₂)_(y)—O—(A¹O)_(x)—R²in which

-   -   R¹ is a C₅- to C₂₁-alkyl or alkenyl radical,    -   R² is a C₁- to C₄-alkyl group,    -   A¹ is C₂- to C₄-alkylene,    -   y is the number 2 or 3 and    -   x has a value from 1 to 6.

Examples of such compounds are the reaction products ofn-butyltriglycolamine of the formula H₂N—(CH₂—CH₂—O)₃—C₄H₉ with methyldodecanoate or the reaction products of ethyltetraglycolamine of theformula H₂N—(CH₂—CH₂—O)₄—C₂H₅ with a standard commercial mixture ofsaturated C₈- to C₁₈-fatty acid methyl esters.

Further suitable nonionic surfactants are also block copolymers ofethylene oxide, propylene oxide and/or butylene oxide (Pluronic® andTetronic® brands from BASF), polyhydroxy or polyalkoxy fatty acidderivatives, such as polyhydroxy fatty acid amides, N-alkoxy- orN-aryloxypolyhydroxy fatty acid amides, fatty acid amide ethoxylates, inparticular terminally capped ones, and fatty acid alkanolamidealkoxylates.

The additional nonionic surfactants are present in the detergentscomprising the cosurfactants used in accordance with the inventionpreferably in an amount of from 0.01 to 30% by weight, in particular 0.1to 25% by weight, especially 0.5 to 20% by weight.

It is also possible to use individual nonionic surfactants or acombination of different nonionic surfactants. The nonionic surfactantsused may come from only one class, in particular only alkoxylated C₈- toC₂₂-alcohols, or surfactant mixtures from different classes can be used.

Suitable anionic surfactants are, for example, fatty alcohol sulfates offatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms,C₁₂-C₁₈-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristylsulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcoholsulfate.

Further suitable anionic surfactants are sulfated ethoxylated C₈- toC₂₂-alcohols (alkyl ether sulfates) or soluble salts thereof. Compoundsof this type are prepared, for example, by firstly alkoxylating a C₈- toC₂₂-, preferably a C₁₀- to C₁₈-alcohol, e.g. a fatty alcohol, and thensulfating the alkoxylation product. For the alkoxylation, preference isgiven to using ethylene oxide, 1 to 50 mol, preferably 1 to 20 mol, ofethylene oxide being used per mole of alcohol. The alkoxylation of thealcohols can, however, also be carried out with propylene oxide on itsown and optionally butylene oxide. Furthermore, also suitable are thosealkylated C₈- to C₂₂-alcohols which contain ethylene oxide and propyleneoxide or ethylene oxide and butylene oxide or ethylene oxide andpropylene oxide and butylene oxide. The alkoxylated C₈- to C₂₂-alcoholscan contain the ethylene oxide, propylene oxide and butylene oxide unitsin the form of blocks or in random distribution. Depending on the natureof the alkoxylation catalyst, alkyl ether sulfates can be obtained witha broad or narrow alkylene oxide homolog distribution.

Further suitable anionic surfactants are alkanesulfonates, such as C₈-to C₂₄-, preferably C₁₀- to C₁₈-alkanesulfonates, and soaps, such as,for example, the Na and K salts of saturated and/or unsaturated C₈- toC₂₄-carboxylic acids.

Further suitable anionic surfactants are linear C₈- toC₂₀-alkylbenzenesulfonates (“LAS”), preferably linear C₉- toC₁₃-alkylbenzenesulfonates and -alkyltoluenesulfonates.

Further suitable anionic surfactants are also C₈- toC₂₄-olefinsulfonates and -disulfonates, which may also representmixtures of alklene- and hydroxyalkanesulfonates or-disulfonates, alkylester sulfonates, sulfonated polycarboxylic acids, alkylglycerolsulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycolether sulfates, paraffinsulfonates having about 20 to about 50 carbonatoms (based on paraffin or paraffin mixtures obtained from naturalsources), alkyl phosphates, acyl isethionates, acyl taurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids orhalf-esters or half-amides thereof, alkylsulfosuccinic acids or amidesthereof, mono- and diesters of sulfosuccinic acids, acyl sarcosinates,sulfated alkyl polyglucosides, alkyl polyglycol carboxylates andhydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the detergent in theform of salts. Suitable cations in these salts are alkali metal ions,such as sodium, potassium and lithium and ammonium salts, such as, e.g.hydroxyethylammonium, di(hydroxyethyl)ammonium andtri(hydroxyethyl)ammonium salts.

The anionic surfactants are present in the detergents comprising thecosurfactants according to the invention preferably in an amount of upto 30% by weight, for example from 0.1 to 30% by weight, especially 1 to25% by weight, in particular 3 to 10% by weight. If C₉- to C₂₀ linearalkyl-benzenesulfonates (LAS) are co-used, these are usually employed inan amount up to 15% by weight, in particular up to 10% by weight.

It is possible to use individual anionic surfactants or a combination ofdifferent anionic surfactants. The anionic surfactants used may be fromonly one class, for example only fatty alcohol sulfates or onlyalkylbenzenesulfonates, although it is also possible to use surfactantmixtures from different classes, e.g. a mixture of fatty alcoholsulfates and alkylbenzenesulfonates.

In addition, the surfactant mixtures comprising the cosurfactants to beused according to the invention can be combined with cationicsurfactants, customarily in an amount up to 25% by weight, preferably 1to 15% by weight, for example C₈- to C₁₆-dialkyldimethylammonium salts,dialkoxydimethylammonium salts or imidazolinium salts with a long-chainalkyl radical; and/or with amphoteric surfactants, customarily in anamount up to 15% by weight, preferably 1 to 10% by weight, for examplederivatives of secondary or tertiary amines, such as, e.g.C₆-C₁₈-alkylbetaines or C₆-C₁₅-alkylsulfobetaines or alkylamidobetainesor amine oxides, such as alkyldimethylamine oxides.

It is also possible to use cationic surfactants as are described in WO99/19435.

The mixtures comprising the cosurfactants to be used in accordance withthe invention are usually combined with builders (sequestering agents),such as, for example, polyphosphates, polycarboxylates, phosphonates,complexing agents, e.g. methylglycinediacetic acid and salts thereof,nitrilotriacetic acid and salts thereof, ethylenediaminetetraacetic acidand salts thereof, and optionally with cobuilders.

Individual builder substances which are highly suitable for thecombination with mixtures comprising the cosurfactants to be used inaccordance with the invention may be listed below:

Suitable inorganic builders are primarily crystalline or amorphousalumosilicates having ion-exchanging properties, such as, in particular,zeolites. Various types of zeolites are suitable, in particular zeolitesA, X, B, P, MAP and HS in their Na form or in forms in which Na ispartially replaced by other cations, such as Li, K, Ca, Mg or ammonium.Suitable zeolites are described, for example, in U.S. Pat. No.4,604,224.

Examples of crystalline silicates which are suitable as builders aredisilicates or phyllosilicates, e.g. δ-Na₂Si₂O₅ or β-Na₂Si₂O₅. Thesilicates can be used in the form of their alkali metal, alkaline earthmetal or ammonium salts, preferably as Na, Li and Mg silicates.Amorphous silicates, such as, for example, sodium metasilicate, whichhas a polymeric structure, or amorphous disilicate can likewise be used.

Suitable carbonate-based inorganic builder substances are carbonates andhydrogencarbonates. These can be used in the form of their alkali metal,alkaline earth metal or ammonium salts. Preference is given to using Na,Li and Mg carbonates or hydrogencarbonates, in particular sodiumcarbonate and/or sodium hydrogencarbonate.

Customary phosphates used as inorganic builders are alkali metalorthophosphates and/or polyphosphates, such as, for example, pentasodiumtriphosphate.

Said builder components can be used individually or in mixtures with oneanother.

In addition, in many cases, it is expedient to add cobuilders to thedetergents comprising the cosurfactants to be used in accordance withthe invention. Examples of suitable substances are listed below:

In a preferred embodiment, the detergents comprising the cosurfactantsto be used in accordance with the invention comprise, in addition to theinorganic builders, 0.05 to 20% by weight, in particular 1 to 10% byweight, of organic cobuilders in the form of low molecular weight,oligomeric or polymeric carboxylic acids, in particular polycarboxylicacids, or phosphonic acids or salts thereof, in particular Na or Ksalts.

Low molecular weight carboxylic acids or phosphonic acids suitable asorganic cobuilders are, for example, phosphonic acids, such as, forexample, 1-hydroxyethane-1,1-diphosphonic acid,amino-tris(methylenephosphonic acid),ethylenediaminetetra-(methylenephosphonic acid),hexamethylenediaminetetra(methylenephosphonic acid) anddiethylenetriaminepenta(methylenephosphonic acid);

-   -   C₄- to C₂₀-di-, -tri- and -tetracarboxylic acids, such as, for        example, succinic acid, propanetricarboxylic acid,        butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and        alkyl- and alkenylsuccinic acids having C₂- to C₁₆-alkyl- or        -alkenyl radicals;    -   C₄- to C₂₀-hydroxycarboxylic acids, such as, for example, malic        acid, tartaric acid, gluconic acid, glutaric acid, citric acid,        lactobionic acid and sucrose mono-, di- and tricarboxylic acid;    -   aminopolycarboxylic acids, such as, for example,        nitrilotriacetic acid, β-alaninediacetic acid,        ethylenediaminetetraacetic acid, serinediacetic acid,        isoserinediacetic acid, alkylethylenediaminetriacetates,        N,N-bis(carboxymethyl)glutamic acid, ethylenediamine-disuccinic        acid and N-(2-hydroxyethyl)iminodiacetic acid, methyl- and        ethylglycinediacetic acid.

Examples of oligomeric or polymeric carboxylic acids which are suitableas organic cobuilders are:

oligomaleic acids, as are described, for example, in EP-A 451508 andEP-A 396303;

co- and terpolymers of unsaturated C₄- to C₈-dicarboxylic acids, thecopolymerized comonomers being monoethylenically unsaturated monomersfrom group (i), given below, in amounts of up to 95% by weight, fromgroup (ii) in amounts of up to 60% by weight and from group (iii) inamounts of up to 20% by weight.

Examples of unsaturated C₄- to C₈-dicarboxylic acids in this context aremaleic acid, fumaric acid, itaconic acid and citraconic acid. Preferenceis given to maleic acid.

Group (i) includes monoethylenically unsaturated C₃-C₈-monocarboxylicacids, such as, for example, acrylic acid, methacrylic acid, crotonicacid and vinylacetic acid. From group (i), preference is given to usingacrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C₂- to C₂₂-olefins,vinyl alkyl ethers having C₁- to C₈-alkyl groups, styrene, vinyl estersof C₁- to C₈-carboxylic acids, (meth)acrylamide and vinylpyrrolidone.From group (ii), preference is given to using C₂- to C₆-olefins, vinylalkyl ethers having C₁- to C₄-alkyl groups, vinyl acetate and vinylpropionate.

If the polymers of group (ii) contain copolymerized vinyl esters, someor all of the latter can also be present in hydrolyzed form to givevinyl alcohol structural units. Suitable co- and terpolymers are known,for example, from U.S. Pat. No. 3,887,806 and DE-A 4313909.

Group (iii) includes (meth)acrylic esters of C₁- to C₈-alcohols,(meth)acrylonitrile, (meth)acrylamides of C₁- to C₈-amines,N-vinylformamide and N-vinylimidazole.

Also suitable as organic cobuilders are homopolymers ofmonoethylenically unsaturated C₃-C₈-monocarboxylic acids, such as, forexample, acrylic acid, methacrylic acid, crotonic acid and vinylaceticacid, in particular acrylic acid and methacrylic acid;

copolymers of dicarboxylic acids, such as, for example, copolymers ofmaleic acid and acrylic acid in the weight ratio 10:90 to 95:5,particularly preferably those in the weight ratio 30:70 to 90:10 withmolar masses of from 1000 to 150 000;

terpolymers of maleic acid, acrylic acid and a vinyl ester of aC₁-C₃-carboxylic acid in the weight ratio 10 (maleic acid):90 (acrylicacid+vinyl ester) to 95 (maleic acid):10 (acrylic acid+vinyl ester),where the weight ratio of acrylic acid to the vinyl ester can varywithin the range from 30:70 to 70:30;

copolymers of maleic acid with C₂-C₈-olefins in the molar ratio 40:60 to80:20, copolymers of maleic acid with ethylene, propylene or isobutenein the molar ratio 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids onto low molecular weightcarbohydrates or hydrogenated carbohydrates, cf. U.S. Pat. No.5,227,446, DE-A 4415623 and DE-A 4313909, are likewise suitable asorganic cobuilders.

Examples of suitable unsaturated carboxylic acids in this context aremaleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid,methacrylic acid, crotonic acid and vinylacetic acid, and also mixturesof acrylic acid and maleic acid which are grafted on in amounts of from40 to 95% by weight, based on the component to be grafted.

For modification, it is additionally possible for up to 30% by weight,based on the component to be grafted, of further monoethylenicallyunsaturated monomers to be present in copolymerized form. Suitablemodifying monomers are the abovementioned monomers of groups (ii) and(iii).

Suitable graft bases are degraded polysaccharides, such as, for example,acidically or enzymatically degraded starches, inulins or cellulose,protein hydrolyzates and reduced (hydrogenated or reductively aminated)degraded polysaccharides, such as, for example, mannitol, sorbitol,aminosorbitol and N-alkylglucamine, and also polyalkylene glycols withmolar masses up to M_(w)=5000, such as, for example, polyethyleneglycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxideor ethylene oxide/propylene oxide/butylene oxide block copolymers andalkoxylated mono- or polyhydric C₁- to C₂₂-alcohols (cf. U.S. Pat. No.5,756,456).

Polyglyoxylic acids suitable as organic cobuilders are described, forexample, in EP-B-001004, U.S. Pat. No. 5,399,286, DE-A-4106355 andEP-A-656914. The end groups of the polyglyoxylic acids may havedifferent structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acidssuitable as organic cobuilders are known, for example, from EP-A-454126,EP-B-511037, WO-A-94/01486 and EP-A-581452.

In particular, polyaspartic acids or cocondensates of aspartic acid withfurther amino acids, C₄- to C₂₅-mono- or -dicarboxylic acids and/or C₄-to C₂₅-mono- or -diamines are also used as organic cobuilders.Particular preference is given to using polyaspartic acids which havebeen prepared in phosphorus-containing acids and modified with C₆- toC₂₂-mono- or -dicarboxylic acids or with C₆- to C₂₂-mono- or -diamines.

Also suitable as organic cobuilders are iminodisuccinic acid,oxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates,aminopolyalkylenephosphonates, polyglutamates, hydrophobically modifiedcitric acid, such as, for example, agaric acid, poly-α-hydroxyacrylicacid, N-acylethylenediaminetriacetates, such as lauroylethylenediaminetriacetate and alkylamides of ethylenediaminetetraaceticacid, such as EDTA-tallow amide.

Furthermore, it is also possible to use oxidized starches as organiccobuilders.

Further suitable (co)builders are described in WO 99/19435.

In a further preferred embodiment, the detergents comprising thecosurfactants to be used in accordance with the invention additionallycomprise, in particular in addition to the inorganic builders, theanionic surfactants and/or the nonionic surfactants, 0.5 to 20% byweight, in particular 1 to 10% by weight, of glycine-N,N-diacetic acidderivatives, as described in WO 97/19159.

It is also frequently expedient to add bleaching systems, consisting ofbleaches, such as, for example, perborate, percarbonate, and optionallybleach activators, such as, for example, tetraacetylethylenediamine,+bleach stabilizers and optionally bleach catalysts to the detergentscomprising the cosurfactants to be used in accordance with theinvention.

In these cases, the detergents comprising the cosurfactants to be usedin accordance with the invention additionally comprise 0.5 to 30% byweight, in particular 5 to 27% by weight, especially 10 to 23% byweight, of bleaches in the form of percarboxylic acids, e.g.diperoxododecanedicarboxylic acid, phthalimidopercaproic acid, ormonoperoxophthalic acid or -terephthalic acid, adducts of hydrogenperoxide with inorganic salts, e.g. sodium perborate monohydrate, sodiumperborate tetrahydrate, sodium carbonate perhydrate or sodium phosphateperhydrate, adducts of hydrogen peroxide with organic compounds, e.g.urea perhydrate, or of inorganic peroxo salts, e.g. alkali metalpersulfates or peroxodisulfates, optionally in combination with 0 to 15%by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 8% byweight, of bleach activators.

Suitable bleach activators are:

-   -   polyacylated sugars, e.g. pentaacetylglucose;    -   acyloxybenzenesulfonic acids and alkali metal and alkaline earth        metal salts thereof, e.g. sodium p-nonanoyloxybenzenesulfonate        or sodium p-benzoyloxybenzene-sulfonate;    -   N,N-diacylated and N,N,N′,N′-tetraacylated amines, e.g.        N,N,N′,N′-tetraacetyl-methylenediamine and -ethylenediamine        (TAED), N,N-diacetylaniline, N,N-diacetyl-p-toluidine or        1,3-diacylated hydantoins, such as        1,3-diacetyl-5,5-dimethylhydantoin;    -   N-alkyl-N-sulfonylcarbonamides, e.g. N-methyl-N-mesylacetamide        or N-methyl-N-mesylbenzamide;    -   N-acylated cyclic hydrazides, acylated triazoles or urazoles,        e.g. monoacetylmaleic hydrazide;    -   O,N,N-trisubstituted hydroxylamines, e.g.        O-benzoyl-N,N-succinylhydroxylamine,        O-acetyl-N,N-succinylhydroxylamine or        O,N,N-triacetylhydroxylamine;    -   N,N′-diacylsulfurylamides, e.g.        N,N′-dimethyl-N,N′-diacetylsulfurylamide or        N,N′-diethyl-N,N′-dipropionylsulfurylamide;    -   acylated lactams, such as, for example, acetylcaprolactam,        octanoylcaprolactam, benzoylcaprolactam or        carbonylbiscaprolactam;    -   anthranil derivatives, such as, for example, 2-methylanthranil        or 2-phenylanthranil;    -   triacyl cyanurates, e.g. triacetyl cyanurate or tribenzoyl        cyanurate;    -   oxime esters and bisoxime esters, such as, for example,        O-acetylacetone oxime or bisisopropyliminocarbonate;    -   carboxylic anhydrides, e.g. acetic anhydride, benzoic anhydride,        m-chlorobenzoic anhydride or phthalic anhydride;    -   enol esters, such as, for example, isopropenyl acetate;    -   1,3-diacyl-4,5-diacyloxyimidazolines, e.g.        1,3-diacetyl-4,5-diacetoxyimidazoline;    -   tetraacetylglycoluril and tetrapropionylglycoluril;    -   diacylated 2,5-diketopiperazines, e.g.        1,4-diacetyl-2,5-diketopiperazine;    -   ammonium-substituted nitriles, such as, for example,        N-methylmorpholinium acetonitrile methylsulfate;    -   acylation products of propylenediurea and        2,2-dimethylpropylenediurea, e.g. tetraacetylpropylenediurea;    -   α-acyloxypolyacylmalonamides, e.g.        α-acetoxy-N,N′-diacetylmalonamide;    -   diacyldioxohexahydro-1,3,5-triazines, e.g.        1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;    -   benz-(4H)1,3-oxazin-4-ones having alkyl radicals, e.g. methyl,        or aromatic radicals, e.g. phenyl, in the 2-position;    -   cationic nitriles, as described in DE-A-101 48 577.

The described bleaching system comprising bleaches and bleach activatorscan optionally also comprise bleach catalysts. Examples of suitablebleach catalysts are quaternized imines and sulfonimines, which aredescribed, for example, in U.S. Pat. No. 5,360,569 and EP-A 453 003.Particularly effective bleach catalysts are manganese complexes, whichare described, for example, in WO-A 94/21777. Where used, such compoundsare incorporated into the detergents in amounts of at most up to 1.5% byweight, in particular up to 0.5% by weight, and in the case of veryactive manganese complexes, in amounts up to 0.1% by weight. Furthersuitable bleach catalysts are described in WO 99/19435.

Further bleaching systems based on arylimidoperalkanoic acids which canbe used are described in EP-A-0 325 288 and EP-A-0 490 409.

Bleach Stabilizer

These are additives which are able to absorb, bind or complex traces ofheavy metals. Examples of additives with a bleach-stabilizing actionwhich can be used according to the invention are polyanionic compounds,such as polyphosphates, polycarboxylates, polyhydroxypolycarboxylates,soluble silicates as completely or partially neutralized alkali metal oralkaline earth metal salts, in particular as neutral Na or Mg saltswhich are relatively weak bleach stabilizers. Strong bleach stabilizerswhich can be used according to the invention are, for example,complexing agents, such as ethylenediamine tetraacetate (EDTA),nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA),β-alaninediacetic acid (ADA), ethylenediamine N,N′-disuccinate (EDDS)and phosphonates, such as ethylenediaminetetramethylenephosphonate,diethylenetriamine-pentamethylenephosphonate orhydroxyethylidene-1,1-diphosphonic acid in the form of the acids or aspartially or completely neutralized alkali metal salts. The complexingagents are preferably used in the form of their Na salts.

As well as the described bleaching system comprising bleaches, bleachactivators and optionally bleach catalysts, the use of systems withenzymatic peroxide release or of photoactivated bleaching systems isalso possible for the detergents comprising the cosurfactants to be usedin accordance with the invention, see e.g. U.S. Pat. No. 4,033,718.

For a number of uses, it is expedient for the detergents comprising thecosurfactants to be used in accordance with the invention to compriseenzymes. Enzymes which are preferably used in detergents are proteases,amylases, lipases and cellulases. Preferred amounts of the enzymes arefrom 0.1 to 1.5% by weight, particularly preferably 0.2 to 1.0% byweight, of the formulated enzyme. Examples of suitable proteases areSavinase and Esperase. A suitable lipase is e.g. Lipolase. A suitablecellulase is e.g. Celluzym. The use of peroxidases for activating thebleaching system is also possible. It is possible to use individualenzymes or a combination of different enzymes. Where appropriate, thedetergent comprising the cosurfactants to be used in accordance with theinvention can also comprise enzyme stabilizers, e.g. calcium propionate,sodium formate or boric acids or salts thereof, and/or antioxidants.

The constituents of detergents are known in principle to the personskilled in the art. The lists, above and below, of suitable constituentsgive merely an illustrative selection of the known suitableconstituents.

In addition to the main components stated hitherto, the detergentscomprising the cosurfactants to be used in accordance with the inventioncan also comprise the following further customary additives in theamounts customary for this purpose:

Known dispersants, such as naphthalenesulfonic acid condensates orpolycarboxylates, soil-carrying agents, soil release agents, such aspolyether esters, incrustation inhibitors, pH-regulating compounds, suchas alkalis or alkali donors (NaOH, KOH, pentasodium metasilicate, sodiumcarbonate) or acids (hydrochloric acid, phosphoric acid, amidosulfuricacid, citric acid), buffer systems, such as acetate or phosphate buffer,ion exchangers, perfume, dyes, graying inhibitors, optical (fluorescent)brighteners, color-transfer inhibitors, such as, for example,polyvinylpyrrolidone, biocides, such as isothiazolinones or2-bromo-2-nitro-1,3-propanediol, hydrotropic compounds as solubilitypromoters or solubilizers, such as cumenesulfonates, toluenesulfonates,short-chain fatty acids, urea, alcohols or phosphoric alkyl/aryl esters,foam regulators for stabilizing or suppressing foam, e.g. silicone oils,skin and corrosion protectants, disinfecting compounds or systems, suchas, for example, those which release chlorine or hypochlorous acid, suchas dichloroisocyanurate or which contain iodine, thickeners andextenders and formulating agents.

Graying Inhibitors and Soil Release Polymers

Suitable soil release polymers and/or graying inhibitors for detergentsare for example:

polyesters of polyethylene oxides with ethylene glycol and/or propyleneglycol and aromatic dicarboxylic acids or aromatic and aliphaticdicarboxylic acids;

polyesters of unilaterally terminally capped polyethylene oxides withdi- and/or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from U.S. Pat. No. 3,557,039,GB-A 1 154 730, EP-A-185 427, EP-A-241 984, EP-A-241 985, EP-A-272 033and U.S. Pat. No. 5,142,020.

Further suitable soil release polymers are amphiphilic graft orcopolymers of vinyl and/or acrylic esters onto polyalkylene oxides (cfU.S. Pat. No. 4,746,456, U.S. Pat. No. 4,846,995, DE-A-37 11 299, U.S.Pat. No. 4,904,408, U.S. Pat. No. 4,846,994 and U.S. Pat. No. 4,849,126)or modified celluloses, such as, for example, methylcellulose,hydroxypropylcellulose or carboxymethylcellulose.

Color Transfer Inhibitors

The color transfer inhibitors used are, for example, homo- andcopolymers of vinylpyrrolidone, of vinylimidazole, of vinyloxazolidoneand of 4-vinylpyridine N-oxide having molar masses of from 15 000 to 100000, and crosslinked finely divided polymers based on these monomers.The use mentioned here of such polymers is known, cf. DE-B-22 32 353,DE-A-28 14 287, DE-A-28 14 329 and DE-A-43 16 023.

Suitable polyvinylpyridinebetaines are described, for example in Tai,Formulating Detergents and Personal Care Products, AOCS Press, 2000,page 113.

In addition to the use in detergents and cleaners for domestic textilewashing, the detergent compositions which can be used according to theinvention can also be used in the field of commercial textile washingand of commercial cleaning. In this field of use, peracetic acid isusually used as bleach, and is added to the wash liquor as an aqueoussolution.

Use in Textile Detergents

A typical pulverulent or granular heavy-duty detergent according to theinvention may, for example, have the following composition:

-   -   0.5 to 50% by weight, preferably 5 to 30% by weight, of at least        one anionic and/or nonionic surfactant, including the        cosurfactants according to the invention,    -   0.5 to 60% by weight, preferably 15 to 40% by weight, of at        least one inorganic builder,    -   0 to 20% by weight, preferably 0.5 to 8% by weight, of at least        one organic cobuilder,    -   2 to 35% by weight, preferably 5 to 30% by weight, of an        inorganic bleach,    -   0.1 to 20% by weight, preferably 0.5 to 10% by weight, of a        bleach activator, optionally in a mixture with further bleach        activators,    -   0 to 1% by weight, preferably up to at most 0.5% by weight, of a        bleach catalyst,    -   0 to 5% by weight, preferably 0 to 2.5%, of a polymeric color        transfer inhibitor,    -   0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of        protease,    -   0 to 1.5% by weight, preferably 0.1 to 1.0% by weight, of        lipase,    -   0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil        release polymer,        ad 100% of customary auxiliaries and adjuncts and water.

Inorganic builders preferably used in detergents are sodium carbonate,sodium hydrogencarbonate, zeolite A and P, and amorphous and crystallineNa silicates, and also phyllosilicates.

Organic cobuilders preferably used in detergents are acrylic acid/maleicacid copolymers, acrylic acid/maleic acid/vinyl ester terpolymers andcitric acid.

Inorganic bleaches preferably used in detergents are sodium perborateand sodium carbonate perhydrate.

Anionic surfactants preferably used in detergents are linear andslightly branched alkylbenzenesulfonates (LAS), fatty alcoholsulfates/ether sulfates and soaps.

Enzymes preferably used in detergents are protease, lipase, amylase andcellulase. For the commercially available enzymes, amounts of from 0.05to 2.0% by weight, preferably 0.2 to 1.5% by weight, of the formulatedenzyme, are generally added to the detergent. Suitable proteases are,for example, Savinase, Desazym and Esperase. A suitable lipase is, forexample, Lipolase. A suitable cellulase is, for example, Celluzym.

Soil release polymers and graying inhibitors preferably used indetergents are graft polymers of vinyl acetate onto polyethylene oxideof molar mass 2500-8000 in the weight ratio 1.2:1 to 3.0:1, polyethyleneterephthalates/oxyethylene terephthalates of molar mass 3000 to 25 000from polyethylene oxides of molar mass 750 to 5000 with terephthalicacid and ethylene oxide and a molar ratio of polyethylene terephthalateto polyoxyethylene terephthalate of from 8:1 to 1:1, and blockpolycondensates according to DE-A-44 03 866.

Color transfer inhibitors preferably used in detergents are soluble NVPhomopolymers and/or vinylpyrrolidone and vinylimidazole copolymers withmolar masses greater than 5000.

The detergents are often in solid, pulverulent form, in which case theyusually additionally comprise customary extenders, which give them goodflowability, dosability and solubility and which prevent caking anddusting, such as sodium sulfate or magnesium sulfate.

The pulverulent or granular detergents according to the invention cancomprise up to 60% by weight of inorganic extenders. However, thedetergents according to the invention preferably have a low content ofextenders and comprise only up to 20% by weight, particularly preferablyonly up to 8% by weight, of extenders.

Detergents comprising the cosurfactants to be used in accordance withthe invention can have various bulk densities in the range from 300 to1200, in particular 500 to 950 g/l. Modern compact detergents usuallyhave high bulk densities and are granular in structure. Compact orultracompact detergents and extrudates have a bulk density of >600 g/l.These are becoming more important.

If they are to be used in liquid form, they may be in the form ofaqueous microemulsions, emulsions or solutions. In liquid detergents,solvents such as ethanol, isopropanol, 1,2-propylene glycol or butylglycol can additionally be used.

In the case of gel detergents thickeners, such as, for example,polysaccharides and/or weakly crosslinked polycarboxylates (for exampleCarbopol® from Goodrich) can additionally be used.

In the case of tablet detergents, tableting auxiliaries, such as, forexample, polyethylene glycols with molar masses of >1000 g/mol, polymerdispersions, and tablet disintegrants such as cellulose derivatives,crosslinked polyvinylpyrrolidone, crosslinked polyacrylates orcombinations of acids, e.g. citric acid+sodium bicarbonate, to name buta few, are additionally required.

The present invention further provides for the use of the mixtures inthe preparation of detergents.

In connection with the present invention, the term “cleaners” isgenerally understood as meaning formulations which are used for cleaninghard surfaces. They are in liquid, gel, paste or solid form. Materialswhich are a type of solid form include powders and compacts, such as,for example granulates and shaped bodies, for example tablets. Examplesinclude hand dishwashing detergents, machine dishwashing detergents,metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners,high-pressure cleaners, alkaline cleaners, acidic cleaners, spraydegreasers, dairy cleaners, upholstery cleaners, plastics cleaners andbath cleaners. They comprise 0.01 to 40% by weight, preferably 0.1 to25% by weight, based on the total formulation, of at least one substanceof the formulae I and/or II. Further constituents are detailed below.

-   -   ionic surfactants, such as, for example, alcohol sulfate/ether        sulfates, alkylbenzene sulfonates, α-olefinsulfonates,        sulfosuccinates, as described above under “detergents”.    -   nonionic surfactants, such as, for example, alcohol alkoxylates,        alkylamine alkoxylates, alkylamide ethoxylates, alkyl        polyglucosides, as described above under “detergents”.    -   amphoteric surfactants, such as, for example, alkylamine oxides,        betaines, as described above under “detergents”.    -   builders, such as, for example, polyphosphates,        polycarboxylates, phosphonates, complexing agents, e.g.        methylglycine diacetic acid and salts thereof, nitrilotriacetic        acid and salts thereof, ethylenediamine tetraacetic acid and        salts thereof, as described above under “detergents”.    -   dispersants, such as, for example, naphthalenesulfonic acid        condensates, polycarboxylates, as described above under        “detergents”.    -   pH-regulating compounds, such as, for example, alkalis (NaOH,        KOH, pentasodium metasilicate) or acids (hydrochloric acid,        phosphoric acid, amidosulfuric acid, citric acid)    -   enzymes, such as, for example lipases, amylases, proteases    -   perfume    -   dyes    -   biocides, such as, for example, isothiazolinones,        2-bromo-2-nitro-1,3-propanediol, as described above under        “detergents”.    -   bleaching systems, consisting of bleaches, such as, for example,        perborate, percarbonate etc., plus bleach activators, such as,        for example, tetraacetylethylenediamine, plus bleach        stabilizers, as described above under “detergents”.    -   Solubilizers, such as, for example cumenesulfonates,        toluenesulfonates, short-chain fatty acids, phosphoric        alkyl/aryl esters    -   solvents, such as, for example, short-chain alkyl oligoglycols,        such as butyl glycol, butyl diglycol propylene glycol monomethyl        ether, alcohols, such as ethanol, isopropanol, aromatic        solvents, such as toluene, xylene, N-alkylpyrrolidones, alkylene        carbonates.

The constituents of cleaners for hard surfaces are known in principle tothe person skilled in the art. The above list represents merely anexemplary section of the constituents.

The cleaners for hard surfaces are usually, but not exclusively, aqueousand are in the form of microemulsions, emulsions or solutions.

Where they are present in solid, pulverulent form, extenders, such as,for example, sodium sulfate, magnesium sulfate, etc. may additionally beused.

In the case of cleaners in the form of tablets, tableting auxiliaries,such as, for example, polyethylene glycols with molar masses >1000g/mol, polymer dispersions etc., and tablet disintegrants, such as, forexample, cellulose derivatives, crosslinked polyvinylpyrrolidone,crosslinked polyacrylates or combinations of acids, e.g. citric acidplus sodium bicarbonate, to name but a few, are additionally required.

Products from the bodycare sector are, for example, shampoos, shower andbath gels, shower and bath lotions, lipsticks and cosmetic formulationswith care and/or conditioning properties, such as styling products.Examples are hair foams, hair gels, hair sprays or after-treatmentcompositions, such as hair tonics, lotions, treatment rinses, treatmentpacks, split-end fluids, hair repair compositions, “hot oil treatments”,shampoos, liquid soaps, care creams, hair-setting compositions, haircolorants and permanent waving compositions. When used in bodycareproducts, the substances according to the formulae I and II have theadvantage that the physiological irritantancy of the surfactant mixturesis moderated and the mucous membranes are protected.

The invention is now illustrated in the examples below.

EXAMPLE 13,5-Bis(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole

0.55 mol of ethylhexanal, 0.25 mol of tris(hydroxymethyl)aminomethaneand 0.25 g of Amberlyst 15 are mixed at room temperature. The reactionmixture is heated to 100° C. at 500 mbar. The water which forms distillsoff over the course of 3 hours. The mixture is then left to cool to roomtemperature and filtered. The reaction product can be used withoutfurther purification.

EXAMPLE 23,5-Bis(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole

The reaction was carried out in a distillation apparatus. 256 g (2.0mol) of 2-ethylhexanal were combined with 121 g (1.0 mol) oftris-hydroxymethylaminomethane at room temperature. The mixture was thenheated to 100° C. at a pressure of 500 mbar. After 1 l at 500 mbar/100°C., the pressure is reduced to 250 mbar until distillate no longerpassed over. The distillate collected was 2-phase. The phase containingethylhexanal was returned to the reaction mixture and stirred again for1 h at 500 bar and 100° C. The product can be used without furtherpurification.

EXAMPLE 3 2-(1-Ethylpentyl)4,4-di(hydroxymethyl)oxazolidine

1.5 mol of 2-ethylhexanal, 1.5 mol of tris(hydroxymethyl)aminomethaneand 1.5 g of Amberlyst 15 were mixed at room temperature with 300 ml oftoluene. The mixture is boiled for three hours with a water separatoruntil no new water is collected. The mixture is then allowed to cool toroom temperature and filtered, and the solvent is evaporated underreduced pressure. The product can be used without further purification.

EXAMPLE 47a-Hydroxymethyl-3,5-di(dodecyl)dihydrooxazolo[3,4-c]oxazole/7a-hydroxymethyl-3,5-di(tetradecyl)dihydrooxazolo[3,4-c]oxazole

0.85 mol of C13/C15-aldehyde mixture, 0.39 mol oftris(hydroxymethyl)aminomethane and 0.4 g of Amberlyst 15 are mixed atroom temperature. The reaction mixture is heated to 100° C. at 500 mbar.The water which forms is distilled over the course of 3 hours. Themixture is then left to cool to room temperature and filtered. Thereaction product can be used without further purification.

EXAMPLE 54,4-Di(hydroxymethyl)-2-dodecyloxazolidine/4,4-di(hydroxymethyl)-2-tetradecyloxazolidine

1.5 mol of C13/C15-aldehyde mixture, 1.5 mol oftris(hydroxymethyl)aminomethane and 1.5 g of Amberlyst® 15 were mixedwith 300 ml of toluene at room temperature. The mixture is boiled forthree hours using a water separator until no more new water iscollected. The mixture is then left to cool to room temperature andfiltered, and the solvent is evaporated under reduced pressure. Theproduct can be used without further purification.

EXAMPLE 6 2-(1-Ethylpentyl)-[1,3]-dioxolan-4-one

0.50 mol (64.1 g) of 2-ethylhexanal and 0.3 g of Amberlyst® 15 wereadded to 150 ml of chloroform at room temperature. The water separatorwas filled with 50 ml of chloroform and the reaction mixture wasrefluxed (93° C.). 0.50 mol (50.0 g) of lactic acid (90% aqueoussolution) was slowly added dropwise and stirred under reflux until 19 mlof H₂O had been separated off. Finally, the Amberlyst® 15 was filteredoff and the product was purified by distillation.

EXAMPLE 7 Hand Dishwashing Detergent

A model formulation comprising 30% by weight of Lutensit® ALBN50 (BASFAG, alkylbenzenesulfate, 50%), 10% by weight of Lutensol® AO7 (BASF AG,C13/15, alcohol ethoxylate, 7 ethylene oxide, 100%), 3% by weight of3,5-bis-(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole isadmixed with various amounts of Lutensol® A3N (BASF AG, C12,14-alcoholethoxylate, 3EO, 100% BASF AG). The resulting mixtures are analyzedusing an Uhbelohde viscometer, spindle 3, shear rate 3 s⁻¹. In parallelexperiments, a corresponding surfactant mixture in which the reactionproduct was replaced by Mazox® LDA (laurylamine oxide, 100%, origin BASFCorporation) and by water were investigated. The results are summarizedin the table. The viscosity increase is most marked for the productaccording to the invention. 0 1 2 4 6 8 % Lutensol ® A3N 892 2900 676030000 172000 3,5-bis-(1-ethylpentyl)-7a-hydroxy-methyldihydrooxazolo[3,4-c]oxazole 1210 905 970 1820 2890 7010 Water2040 2500 2910 5760 12700 19200 Mazox LDA Oxide w.s.

EXAMPLE 8 Hand Dishwashing Detergent

Foam stabilization with3,5-bis(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole.

A model formulation comprising 30% by weight of Lutensit® ALBN50(alkylbenzenesulfate, 50%), 10% by weight of Lutensol® AO7 (C13/15,alcohol ethoxylate, 7 ethylene oxide, 100%), 3% by weight of3,5-bis(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole and3% by weight of Lutensol A3N (C12,14-alcohol ethoxylate, 3EO, 100%) isdiluted to 2% by weight of surfactant. In a beaker (5 l in volume,filled to 2 l), this surfactant solution is added to the foam bystirring. When a stable state has been established, fresh olive oil isadded dropwise until the foam has disappeared. The amount of oilnecessary for this is a measure of the stability of the foam. Inparallel experiments, a corresponding surfactant mixture in which thereaction product was replaced by Mazox® LDA (laurylamine oxide, 100%)and by water were investigated. The results are summarized in the table.Consumption of olive Additive oil3,5-Bis(1-ethylpentyl)-7a-hydroxymethyl- 37 mldihydrooxazolo[3,4-c]oxazole + 3 EO Mazox ® LDA 28 ml Water 27 ml

1. A cyclic aldehyde derivative of the formulae

in which the symbols X, Y, Z and R¹ to R¹³ have the following meanings:R¹ is hydrogen or a linear or branched, substituted or unsubstitutedC₃-C₂₉-alkyl group or a linear or branched, substituted or unsubstitutedC₃-C₂₉-alkenyl group, where one or more carbon atoms in the alkyl oralkenyl chain may be replaced by —O—, —NR¹⁴, —C(O)NR¹⁵— or —S— and —O—O—and —S—S— are excluded; R² is hydrogen or —CH₃; R³, R⁴, R⁵ and R⁶ are,independently of one another, chosen from the group of substituentsconsisting of: H; —CN; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; C₆H₅, in whichone or more hydrogens may be replaced by substituents;

and C₁-C₅-alkyl groups which, at any desired point in the chain, mayhave 1 to 4 substituents from the group —OH; —SH; —CN; NR¹⁶R¹⁷; —OR²²;or 1 to 2 substituents from the group consisting of —C(O)OH; —C(O)OR¹⁸;—C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; C₆H₅, in which oneor more hydrogens may be replaced by substituents; and

or one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O; R⁷, R⁸, R⁹ andR¹⁰ are, independently of one another, chosen from the group ofsubstituents consisting of: H; —CN; —NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸;—C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; C₆H₅, in which one or morehydrogens may be replaced by substituents;

and C₁-C₅-alkyl groups which, at any desired point on the chain, mayhave 1 to 4 substituents from the group —OH; —SH; —CN; NR¹⁶R¹⁷; —OR²²;or 1 to 2 substituents from the group consisting of —C(O)OH; —C(O)OR¹⁸;—C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ³¹ ; —OPO₃ ²⁻; OPO(OR²¹)₂; C₆H₅, in whichone or more hydrogens may be replaced by substituents; and

R¹¹ has, independently, the same meaning as R¹; R¹² has, independently,the same meaning as R²; R¹³ has, independently, the same meaning as R³,R⁴, R⁵or R⁶; R¹⁴ is a linear or branched C₁-C₄-alkyl group; R¹⁵ ishydrogen or a linear or branched C₁-C₄-alkyl group; R¹⁶, R¹⁷ are,independently of one another, hydrogen or a linear or branchedC₁-C₄-alkyl group; R¹⁸ is chosen from the group consisting ofC₁-C₆-alkyl groups and ethyleneoxy groups —(CH₂—CH₂O—)_(p); R¹⁹, R²⁰have, independently, the same meaning as R¹⁶, R¹⁷; R²¹ is a C₁-C₄-alkylgroup or —C₆H₅; R²² is chosen from the group consisting of C₁-C₁₀-alkylgroups, acyl groups —C(O)R²³ and the group consisting of ethyleneoxygroups —(CH₂—CH₂O—)_(q), propyleneoxy groups —(CH(CH₃)—CH₂O—)_(r),butyleneoxy groups —(C₄H₉O—)_(s), and alkyleneoxy groups containing atleast two of the abovementioned groups in the form of block or randomcopolymers and containing a total of at most 15 alkyleneoxy units; R²³is a C₁-C₁₈-alkyl group; X and Y in formula I and II are, independentlyof one another, O, S, or NR²⁴, Z in formula II is N; R²⁴ is hydrogen ora C₁-C₄-alkyl group; l, m and n are, independently of one another, 0 or1; p is an integer from 1 to 15; q is an integer from 1 to 15; r is aninteger from 1 to 15; s is an integer from 1 to 15; and where thealiphatic moiety of the compounds of the formula I or II which does notoriginate from the feed aldehyde, in cases where X, Y are ═O and R³, R⁴or R⁵, R⁶ are ═O, must have at least 2 carbon atoms, and in all othercases must have at least 3 carbon atoms.
 2. A compound as claimed inclaim 1 in which one, two or more or all of the symbols X, Y and Z, one,two or more or all of the substituents R¹ to R¹³, and one or more of thesymbols l, m and n have the following meanings: R¹ is a linear orbranched C₅-C₁₇-alkyl group or a linear or branched C₃-C₁₇-alkenylgroup, where one or more carbon atoms in the alkyl chain may be replacedby O or NR¹⁴ and —O—O— is excluded; R² is —H; R³, R⁴, R⁵ and R⁶ are,independently of one another, chosen from the group consisting of: —H;—C(O)OH; —C(O)OR¹⁸;

and C₁-C₅-alkyl groups which, at any desired position on the chain, mayhave 1 or 2 substituents from the group —OH; —CN; NR¹⁶R¹⁷; —OR²²; or 1substituent from the group consisting of —C(O)OH; —C₆H₅, in which one ormore hydrogens may be replaced by substituents; and

or one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O; R⁷, R⁸, R⁹ andR¹⁰ are, independently of one another, chosen from the group consistingof: —H; —NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸;

and C₁-C₅-alkyl groups which, at any desired position on the chain, mayhave 1 or 2 substituents from the group —OH; —CN; NR¹⁶R¹⁷; —OR²²; or 1substituent from the group consisting of —C(O)OH; —C₆H₅, in which one ormore hydrogens may be replaced by substituents; and

R¹¹ has, independently, the same meaning as R¹; R¹² has, independently,the same meaning as R²; R¹³ has, independently, the same meaning as R³,R⁴, R⁵ or R⁶; R¹⁴ is a linear or branched C₁-C₄-alkyl group; R¹⁶, R¹⁷are, independently of one another, hydrogen or a linear or branchedC₁-C₄-alkyl group; R¹⁸ is chosen from the group consisting ofC₁-C₆-alkyl groups and ethyleneoxy groups —(CH₂—CH₂O—)_(p); R²² ischosen from the group consisting of C₁-C₄-alkyl groups, acyl groups—C(O)R²³ and the group consisting of ethyleneoxy groups—(CH₂—CH₂O—)_(q), propyleneoxy groups —(CH(CH₃)—CH₂O—)_(r) andbutyleneoxy groups —(C₄H₉O—)_(s), and mixed alkyleneoxy groups; R²³ is aC₁-C₁₈-alkyl group; X and Y in the formula I and II are, independentlyof one another, O or NR²⁴, Z in formula II is N; R²⁴ is hydrogen or aC₁-C₄-alkyl group; l, m and n are, independently of one another, 0 or 1;p is an integer from 1 to 15; q is an integer from 1 to 10; r is aninteger from 1 to 10; s is an integer from 1 to 10; and where thealiphatic moiety of the compounds of the formula I or II which does notoriginate from the feed aldehyde, in cases where X, Y are ═O and R³, R⁴or R⁵, R⁶ are ═O, must have at least 2 carbon atoms, and in all othercases must have at least 3 carbon atoms.
 3. A compound as claimed inclaim 1 or 2, in which one, two or more or all of the symbols X, Y, Zand l, m, and n and also one, two or more or all of the substituents R¹to R¹³ have the following meanings: R¹ is a linear or branchedC₅-C₁₇-alkyl group or a linear or branched C₅-C₁₇-alkenyl group; R² is—H; R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from thegroup consisting of: —H; —C(O)OH; and C₁-C₃-alkyl groups which can have,at any desired point on the chain, 1 or 2 substituents from the group—OH; —NR¹⁶R¹⁷; —OR²²; or 1 substituent from the group consisting of—C(O)OH; and

or one of the substituent pairs R³, R⁴ and R⁵, R⁶ is ═O; R⁷, R⁸, R⁹ andR¹⁰ are, independently of one another, chosen from the group consistingof: —H; —NR¹⁶R¹⁷; —C(O)OH; and C₁-C₃-alkyl groups which, at any desiredpoint on the chain, can have 1 or 2 substituents from the group —OH;NR¹⁶R¹⁷; or 1 substituent from the group consisting of —C(O)OH; and

R¹¹ has, independently, the same meaning as R¹; R¹² has, independently,the same meaning as R²; R¹³ has, independently, the same meaning as R³,R⁴, R⁵ or R⁶; R¹⁶, R¹⁷ are, independently of one another, hydrogen or alinear or branched C₁-C₄-alkyl group; R²² is chosen from the groupconsisting of C₁-C₄-alkyl groups, acyl groups —C(O)R²³ and the groupconsisting of ethyleneoxy groups —(CH₂—CH₂O—)_(q), propyleneoxy groups—(CH(CH₃)—CH₂O—)_(r) and butyleneoxy groups —(CH₂CH(C₂H₅—O—)s-, andmixed alkyleneoxy groups; R²³ is a C₁-C₁₈-alkyl group; X and Y informula I and II are, independently of one another, O or NR²⁴, Z informula II is N; R²⁴ is hydrogen or a C₁-C₄-alkyl group; l, m and n are,independently of one another, 0 or 1; q is an integer from 1 to 10; r isan integer from 1 to 10; s is an integer from 1 to 10; and where thealiphatic moiety of the compounds of the formula I or II which does notoriginate from the feed aldehyde in cases where X, Y are ═O and R³, R⁴or R⁵, R⁶ are ═O must have at least 2 carbon atoms, and in all othercases must have at least 3 carbon atoms.
 4. A compound as claimed in anyof claims 1 to 3, in which one, two or more or all of the symbols X, Y,Z and l, m, and n and also one, two or more or all of the substituentsR¹ to R¹³ have the following meanings: R¹ is a linear or branchedC₃-C₂₁-alkyl group or a linear or branched C₃-C₂₁-alkenyl group; R² is—H; R³, R⁴, R⁵ and R⁶ are, independently of one another, chosen from thegroup consisting of: —H; —C(O)OH; and C₁-C₃-alkyl groups which may have,at any desired point on the chain, 1 or 2 substituents from the group—OH; —NR¹⁶R¹⁷; —OR²²; or 1 substituent of the type —C(O)OH; or one ofthe substituent pairs R³, R⁴ and R⁵, R⁶ is ═O; R⁷, R⁸, R⁹ and R¹⁰ are,independently of one another, chosen from the group consisting of: —H;—NR¹⁶R¹⁷; —C(O)OH; and C₁-C₃-alkyl groups which may have, at any desiredpoint on the chain, 1 or 2 substituents on the group —OH; NR¹⁶R¹⁷; or 1substituent of the type —C(O)OH; R¹¹ has, independently, the samemeaning as R¹; R¹² has, independently, the same meaning as R²; R¹³ has,independently, the same meaning as R³, R⁴, R⁵ or R⁶; R¹⁶, R¹⁷ are,independently of one another, hydrogen or a linear or branchedC₁-C₄-alkyl group; R²² is chosen from the group consisting ofC₁-C₄-alkyl groups and ethyleneoxy groups —(CH₂—CH₂O—)_(q); X and Y informula I and II are, independently of one another, O, S, or NR²⁴, Z informula II is N; R²⁴ is hydrogen or a C₁-C₄-alkyl group; l, m and n are,independently of one another, 0 or 1; q is an integer from 3 to 8; andwhere the aliphatic moiety of the compounds of the formula I or II whichdoes not originate from the feed aldehyde in cases where X, Y are ═O andR³, R⁴ or R⁵, R⁶ are ═O must have at least 2 carbon atoms, and in allother cases must have have at least 3 carbon atoms.
 5. As compound asclaimed in claim 1: 2-(1-ethylpentyl)-[1,3]-dioxolan-4-one (1);3,5-bis(1-ethylpentyl)-7a-hydroxymethyldihydrooxazolo[3,4-c]oxazole (2);7a-hydroxymethyl-3,5-di(nonyl)dihydrooxazolo[3,4-c]oxazole (3);2-(1-ethylpentyl)4,4-di(hydroxymethyl)oxazolidine (4);4,4-di(hydroxymethyl)-2-nonyloxazolidine (5);2-(1-propylhexyl)4,4-di(hydroxymethyl)oxazolidine (6);7a-hydroxymethyl-3,5-di(dodecyl)dihydrooxazolo[3,4-c]oxazole (7);7a-hydroxymethyl-3,5-di(tetradecyl)dihydrooxazolo[3,4-c]oxazole (8);7a-hydroxymethyl-3,5-di(undecyl)dihydrooxazolo[3,4-c]oxazole (9);7a-hydroxymethyl-3,5-di(tridecyl)dihydrooxazolo[3,4-c]oxazole (10);4,4-di(hydroxymethyl)-2-dodecyloxazolidine (11);4,4-di(hydroxymethyl)-2-tetradecyloxazolidine (12);4,4-di(hydroxymethyl)-2-undecyloxazolidine (13);4,4-di(hydroxymethyl)-2-tridecyloxazolidine (14);2-(1-propylhexyl)-[1,3]-dioxolan-4-one (15)2-(1-propylhexenyl)-[1,3]-dioxolan-4-one (16)7a-hydroxymethyl-3,5-di(1-propylhexenyl)dihydrooxazolo[3,4-c]oxazole(17) 4,4-di(hydroxymethyl)-2-(1-propylhexenyl)oxazolidine (18) mixturesof (7) and (8); mixtures of (11) and (12) mixtures of (9) and (10);mixtures of (13) and (14); adducts of one of the substances (1) to (18)having 3 to 10 ethylene oxide units and mixtures thereof.
 6. A compoundas claimed in any of claims 1 to 5, wherein the substituent R¹ has anaverage degree of branching from 0 to 2.5, preferably 0.2 to 1.6.
 7. Aprocess for the preparation of a compound as claimed in any of claims 1to 6, which comprises, in a condensation reaction known per se, reactingthe respective aldehyde or an aldehyde mixture and the polyfunctionalcompound to be reacted therewith and comprising at least two identicalor different functional groups chosen from hydroxyl, diol, carboxyl andprimary and secondary amino functions or a mixture of polyfunctionalcompounds, together, optionally in the presence of a suitable acid.
 8. Aprocess as claimed in claim 7, wherein Lewis or Brönsted acids known perse are used in liquid or solid form, preferably sulfuric acid,p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt or acidicion exchangers.
 9. A process as claimed in claim 7 or 8, wherein thealdehyde used is a linear or branched aliphatic C₄-C₃₀-aldehyde,preferably a C₆-C₁₈-aldehyde, having an average degree of branching offrom 0 to 2.5, preferably 0.2 to 1.6.
 10. A process as claimed in any ofclaims 7 to 9, wherein the polyfunctional compound is a compound chosenfrom the following groups: linear and branched aliphatic C₃-C₆-polyolswith at least two hydroxyl functions, preferably 2 to 5 hydroxylfunctions, in particular 2 to 4 hydroxyl functions, in which, inaddition to the hydroxyl functions, further functional groups may bepresent which are chosen from the group —SH; —CN; NR¹⁶R¹⁷; —C(O)OH;—C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²;C₆H₅, in which one or more hydrogens may be replaced by substituents;and

linear and branched aliphatic C₃-C₆-alkanolamines with at least oneprimary or secondary amino function and a hydroxyl function, in which amaximum of 4 further hydroxyl or amino functions may be present,preferably exactly one amino function, and further substituents may bepresent from the group: —SH; —CN; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰;—OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one ormore hydrogens may be replaced by substituents; and

linear and branched aliphatic C₃-C₆-thiols with one thiol function andone hydroxyl function, in which four further hydroxyl or thiol functionsmay be present, preferably the thiol has exactly one SH function andfurther substituents may be present from the group: —OH; —SH; —CN;NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹⁵R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻;OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or more hydrogens may be replacedby substituents; and

linear and branched aliphatic C₃-C₆-hydroxycarboxylic acids with onehydroxyl function and one carboxyl function in which four furtherhydroxyl or carboxyl functions may be present, preferably the moleculehas exactly one carboxyl function and further substituents may bepresent from the group: —SH; —CN; NR¹⁶R¹⁷; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰;—OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one ormore hydrogens may be replaced by substituents; and

linear and branched aliphatic C₃-C₆-diamines with 2 to 6 primary orsecondary amino functions, preferably 2 to 4 primary or secondary aminofunctions, and further substituents may be present from the group: —OH;—SH; —CN; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻; —SO₃ ⁻; —OPO₃ ²⁻;OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or more hydrogens may be replacedby substituents; and

linear and branched aliphatic C₃-C₆-aminothiols with at least oneprimary or secondary amino function and one thiol function, preferablythe aminothiol used has exactly one primary or secondary amino functionand exactly one thiol function, and further substituents may be presentfrom the group: —OH; —CN; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰; —OSO₃ ⁻;—SO₃ ⁻; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or morehydrogens may be replaced by substituents; and

linear and branched aliphatic C₃-C₆-amino acids with at least oneprimary or secondary amino function and a carboxyl function, preferablyexactly one primary or secondary amino function; linear and branchedaliphatic C₃-C₆-dithiols with at least two thiol functions, preferablyexactly two thiol functions, and further substituents may be presentfrom the group: —OH; —CN; NR¹⁶R¹⁷; —C(O)OH; —C(O)OR¹⁸; —C(O)NR¹⁹R²⁰;—OSO₃ ⁻; —SO₃—; —OPO₃ ²⁻; OPO(OR²¹)₂; —OR²²; —C₆H₅, in which one or morehydrogens may be replaced by substituents; and


11. A process as claimed in any of claims 7 to 10, wherein the polyolused is glycerol, tartaric acid, diethyl tartrate, trimethylolpropane,fructose, cyclohexanediol, sucrose, tetrahydroxybutane, the alkanolamineused is trimethylolmethylamine, diethanolamine, propanolamine,dipropanolamine, amino sugars, the thiol used is mercaptoethanol,mercaptolactic acid, mercaptoglycolic acid, thiosalicylic acid,mercaptosuccinic acid, 3-mercapto-1,2-propanediol, cysteine,N-acetylcysteine, 3-mercaptopropionic acid, penicillamine, thehydroxycarboxylic acid used is lactic acid, citric acid, glycolic acid,tartaric acid, glyceric acid, maleic acid, salicylic acid, the diamineused is propylenediamine, diethylenetriamine, triethylenetetramine,N-aminopropylethylenediamine (N₃-amine),N,N′-bis(aminopropyl)ethylenediamine (N₄ amine),hydroxyethylethylenediamine, the aminothiol used is cysteine, tyrosine,mercaptopropylamine, the amino acid used is aminodiacetic acidHN(CH₂CO₂H)₂, ethylenediaminetriacetic acid, alanine, arginine,asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine,histidine, isoleucine, leucine, lysine, methionine, phenylalanine,proline, serine, threonine, tryptophan, tyrosine, valine, orN-phosphonomethylglycine.
 12. The use of a substance as claimed in anyof claims 1 to 6 or a mixture thereof as cosurfactant.
 13. A householddetergent, household cleaner, body-cleansing composition or bodycarecomposition comprising at least one compound as claimed in any of claims1 to
 6. 14. A detergent as claimed in claim 13 in solid, liquid, gel orpaste form, preferably in the form of a powder, compact, granulate,tablet or gel.
 15. A detergent as claimed in claim 13 or 14 comprising0.1 to 40% by weight, in particular 0.5 to 30% by weight, veryparticularly 1 to 20% by weight, based on the total amount of theformulation, of at least one compound as claimed in any of claims 1 to6.
 16. A household cleaner as claimed in claim 13 in liquid, gel, orsolid form, preferably in the form of a liquid, gel, powder or compact.17. A household cleaner as claimed in claim 16 in the form of a handdishwashing detergent, machine dishwashing detergent, metal degreaser,glass cleaner, floor cleaner, all-purpose cleaner, high-pressurecleaner, alkaline cleaner, acidic cleaner, spray degreaser, dairycleaner, upholstery cleaner, plastics cleaner and bath cleaner.
 18. Ahousehold cleaner as claimed in claim 16 or 17 comprising 0.01 to 40% byweight, preferably 0.1 to 25% by weight, based on the overallformulation, of at least one substance as claimed in any of claims 1 to5.
 19. A body-cleansing composition or bodycare composition in the formof a shampoo, shower gel or bath gel, shower lotion or bath lotion, alipstick, a cosmetic formulation with care and/or conditioningproperties or a styling product, in particular a liquid soap, a carecream, a hair foam, hair gel, hairspray or after-treatment composition,a hair tonic, a lotion, treatment rinse, treatment pack, split-endfluid, hair repair composition, “hot oil treatments”, hair-settingcomposition, hair colorant or permanent waving composition.